Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01C—RESISTORS
  • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01C—RESISTORS
  • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
  • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
  • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
  • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
  • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49082—Resistor making
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12014—All metal or with adjacent metals having metal particles
  • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
  • Y10T428/12049—Nonmetal component

Definitions

• the invention relates to thick film resistor compositions and especially those which are fireable in low oxygen-containing atmospheres.
• Thick film resistor composites generally comprise a mixture of electrically conductive material finely dispersed in an insulative glassy phase matrix. Resistor composites are then terminated to a conductive film to permit the resultant resistor to be connected to an appropriate electrical circuit.
• the conductive materials are usually sintered particles of noble metals. They have excellent electrical characteristics; however, they are expensive. Therefore, it would be desirable to develop circuits containing inexpensive conductive materials and compatible resistors having a range of stable resistance values.
• nonnoble metal conductive phases such as Cu, Ni, Al, etc. are prone to oxidation. During the thick film processing, they continue to oxidize and increase the resistance values. However, they are relatively stable if the processing can be carried out at low oxygen partial pressure or "inert" atmosphere.
• low oxygen partial pressure is defined as the oxygen partial pressure that is lower than the equilibrium oxygen partial pressure of the system consisting of the metal conductive phase and its oxide at the firing temperature. Therefore, development of compatible resistor functional phases which are capable of withstanding firing in a low oxygen partial pressure without degradation of properties is the prime objective in this technology.
• the phases must be thermodynamically stable after the processing of the resistor film and noninteractive to the nonprecious metal terminations when they are cofired in an "inert" or low oxygen partial pressure atmosphere.
• the major stability factor is the temperature coefficient of resistance (TCR).
• TCR temperature coefficient of resistance
• the invention is directed to a thick film resistor composition for firing in a low oxygen-containing atmosphere comprising finely divided particles of (a) an anion-deficient semiconductive material consisting essentially of a refractory metal nitride, oxynitride or mixture thereof (b) one or more metallic conductive materials or precursors thereof and (c) a nonreducing glass having a softening point below that of the semiconductive material, dispersed in (d) organic medium.
• an anion-deficient semiconductive material consisting essentially of a refractory metal nitride, oxynitride or mixture thereof
• b one or more metallic conductive materials or precursors thereof
• a nonreducing glass having a softening point below that of the semiconductive material, dispersed in (d) organic medium.
• the invention is directed to a resistor element comprising a printed layer of the above-described composition which has been fired in a low oxygen-containing atmosphere to effect volatilization of the organic medium and liquid phase sintering of the glass.
• Huang et al. in U.S. 3,394,087 discloses resistor composition comprising a mixture of 50-95% wt. vitreous glass frit and 50-5% wt. of a mixture of refractory metal nitride and refractory metal particles. Disclosed are nitrides ofTi, Zr, Hf, Va, Nb, Ta, Cr, Mo and W. The refractory metals include Ti, Zr, Hf, Va, Nb, Ta, Cr, Mo and W.
• a resistor composition comprising a vitreous glass frit and fine particles of Group IV, V or VI metal borides such as CrB 2 , ZrB 2 , MoBr 2 , TaB 2 and TiB 2 .
• a resistor composition comprising 25-90 wt. % borosilicate glass and 75-10 wt.% of a metal silicide.
• metal silicides are WSi 2 , MoSi 2 , VaSi 2 , TiSi 2 , ZrSi 2 , CaSi 2 and TaSi 2 . Boonstra et al. in U.S.
• a resistor composition comprising a metal rhodate (Pb 3 Rh 7 O 5 or Sr 3 RhO 15 ), glass binder and a metal oxide TCR driver.
• the metal oxide corresponds to the formula Pb 2 M 2 O 6 ⁇ 7 , wherein M is Ru, Os or lr.
• Hodge in U.S. 4,137,519 discloses a resistor composition comprising a mixture of finely divided particles of glass frit and W 2 C 3 and W0 3 with or without W metal.
• Shapiro et al. in U.S. 4,168,344 disclose resistor compositions comprising a mixture of finely divided particles of glass frit and 20-60% wt.
• Ni, Fi and Co in the respective proportions of 12-75/5-60/5-70% vol.
• the metals form an alloy dispersed in the glass.
• resistor compositions comprising a mixture of vitreous glass frit having fine particles of Ta 2 N dispersed therein.
• the composition may also contain fine particles of B, Ta, Si, ZrO 2 and MgZr0 3 .
• Merz et al. in U.S. 4,209,764 disclose a resistor composition comprising a mixture of finely divided particles of vitreous glass frit, Ta metal and up to 50% wt.
• a resistor composition comprising a mixture of finely divided particles of Sn0 2 , a primary additive of oxides of Mn, Ni, Co or Zn and a secondary additive of oxides of Ta, Nb, W or Ni.
• 4,384,989 is directed to a conductive ceramic composition comprising BaTi0 3 , a doping element such as Sb, Ta or Bi and an additive such as SiN, TiN, ZrN or SiC, to lower the resistivity of the composition.
• Japanese patent application 58-36481 to Hattori et al. is directed to a resistor composition comprising Ni x Siy or Ta x Siy and any glass frit ("... there is no specification regarding its composition or method of preparation.”).
• US-A-4 098 725 is directed to low thermally expansive ceramics (TCE) and in particular to low TCE electroconductive composites consisting of a continuous phase of (1) low TCE ceramic material, (2) a negative TCE ceramic material dispersed in (3) an electroconductive substance, among which are mentioned TiN and SiC.
• US-A-3 394 087 is directed to enamel resistors containing quite large amounts of glass and rather small amounts of a mixture of refractory metal nitrides and refractory metal.
• compositions of the invention are directed to heterogeneous thick film compositions which are suitable for forming microcircuit resistor components which are to undergo firing in a low oxygen-containing atmosphere.
• the resistor compositions of the invention therefore contain the following three basic components: (1) one or more anion-deficient semiconductive materials which are refractory metal nitrides, oxides or mixtures thereof; (2) one or more metallic conductive materials or precursors thereof; and (3) an insulative glass binder, all of which are dispersed in (4) an organic medium.
• the resistance values of the composition are adjusted by changing the relative proportions of the semiconductive/conductive/insulative phases present in the system.
• Supplemental inorganic materials may be added to adjust the temperature coefficient of resistance. After printing over alumina or similar ceramic substrates and firing in a low oxygen partial pressure atmosphere, the resistor films provide a wide range of resistance values and low temperature coefficient of resistance depending on the ratio of the functional phases.
• the anion-deficient semiconductive materials which can be used in the compositions of the invention are the nitrides and oxynitrides of refractory metals and mixtures thereof.
• the refractory metals are Si, AI, Zr, Hf, Ta, W and Mo.
• the nitrides which can be used all have defect structures in that they contain vacant lattice sites and are anion-deficient.
• the lattice also contains oxygen atoms.
• the preferred nitride for use in the invention is a-Si 3 N 4 which corresponds to the formula SI 3 N7 4-x ⁇ x , in which 0 represents a lattice vacancy and x denotes the molar proportions of such vacancies.
• silicon nitrides are made by a reaction bonding process which involves two-stage heating of silicon metal in a nitrogen atmosphere.
• the silicon is heated for on the order of 24 hours below the melting point of silicon (ca. 1400°C).
• the silicon is heated for a similar period of time above the melting point of silicon.
• the first stage results in the formation of an interlocking acicular structure which is generally a-Si 3 N 4 .
• the interlocking structure rapidly changes to a granular structure ((3-Si 3 N 4 ).
• Most commercially available Si 3 N 4 is a mixture of the a and ⁇ nitride forms.
• Refractory metal nitrides of fine particle size, particularly pure a-Si 3 N 4 are prepared by the reduction-nitridation of amorphous metal oxides in ammonia gas.
• the amorphous metal oxides are prepared by hydrolysis of the corresponding metal alkoxides, which have been dried in air at 125-160°C and then heated at about 1350°C in a flowing stream of ammonia. Further details of this method can be obtained in M. Hoch and K. M. Nair, Bulletin American Ceramic Soc., 58, 1979, p. 187.
• Other conventional methods of preparing Si 3 N 4 are described by G. V. Samsonov, Silicides and Their Uses in Engineering, Foreign Technology Div., U.S. Air Force Systems Command, WPAFB, OH (1962).
• sialon which is an oxynitride solid solution of silicon, aluminum, nitrogen and oxygen.
• TCR drivers may be used in the compositions of the invention to adjust TCR values and, in some instances, resistance values as well.
• Such materials include AIN, Mn 2 N 3 and other metal nitrides, alpha, chi and gamma A1 2 0 3 , AIOOH, Al 2 O 3 ⁇ Si0 2 and silicides such as TaSi 2 and NiS 2 .
• the third major component present in the invention is one or more of insulative phases.
• the glass frit can be of any composition which has a melting temperature below that of the semiconductive and/or conductive phases and which contains nonreducible inorganic ions or inorganic ions reducible in a controlled manner.
• compositions are alumino borosilicate glass containing Ca2+, Ti4+, Zr 4+ ; alumino borosilicate glass containing Ca2+, Zn 2+ , Ba2+, Zr 4+ , Na + , borosilicate glass containing Bi3+, Pb 2+ ; alumino borosilicate glass containing Ba2+, Ca2+, Zr4+, Mg 2+ , Ti4+; and lead germanate glass, etc. Mixtures of these glasses can also be used.
• inorganic ions reduce to metals and disperse throughout the system and become a conductive functional phase.
• glasses containing metal oxides such as ZnO, SnO, Sn0 2 , etc.
• These inorganic oxides are nonreducible thermodynamically in the nitrogen atmosphere.
• the "border line" oxides are buried or surrounded by carbon or organics, the local reducing atmosphere developed during firing is far below the oxygen partial pressure of the system.
• the reduced metal is either evaporated and redeposited or finely dispersed within the system. Since these fine metal powders are very active, they interact with or diffuse into other oxides and form metal rich phases.
• the glasses are prepared by conventional glass making techniques, by mixing the desired components in the desired proportions and heating the mixture to form a melt. As is well known in the art, heating is conducted to a peak temperature and for a time such that the melt becomes entirely liquid and homogeneous.
• the components are premixed by shaking in a polyethylene jar with plastic balls and then melted in a crucible at up to 1200°C, depending on the composition of the glass.
• the melt is heated at a peak temperature for a period of 1-3 hours.
• the melt is then poured into cold water.
• the maximum temperature of the water during quenching is kept as low as possible by increasing the volume of water to melt ratio.
• the crude frit after separation from water is freed from residual water by drying in air or by displacing the water by rinsing with methanol.
• the crude frit is then ball milled for 3-5 hours in porcelain containers using alumina balls.
• the slurry is dried and Y-milled for another 24-48 hours depending on the desired particle size and particle size distribution in polyethylene lined metal jars using alumina cylinders. Alumina picked up by the materials, if any, is not within the observable limit as measured by X-ray diffraction analysis.
• the excess solvent is removed by decantation and the frit powder is then screened through a 325 mesh screen at the end of each milling process to remove any large particles.
• the major properties of the frit are: it aids the liquid phase sintering of the inorganic crystalline particulate matters; some inorganic ions present in the frit reduce to conductive metal particles during the firing at the reduced oxygen partial pressure; and part of the glass frit form the insensitive functional phase of the resistor.
• the semiconductive resistor materials generally have quite high resistivities and/or highly negative HTCR (Hot Temperature Coefficient of Resistance) values
• various TCR drivers may be used.
• Preferred conductive materials for use in the invention are Ru0 2 , Ru, Cu, Ni, and Ni 3 B. Other compounds which are precursors of the metals under low oxygen containing firing conditions can also be used. Alloys of the metals are useful as well.
• inorganic particles are mixed with an inert liquid medium (vehicle) by mechanical mixing (e.g., on a roll mill) to form a pastelike composition having suitable consistency and rheology for screen printing.
• a pastelike composition having suitable consistency and rheology for screen printing.
• the latter is printed as a "thick film" on conventional ceramic substrates in the conventional manner.
• the main purpose of the organic medium is to serve as a vehicle for dispersion of the finely divided solids of the composition in such form that it can readily be applied to ceramic or other substrates.
• the organic medium must first of all be one in which the solids are dispersible with an adequate degree of stability.
• the rheological properties of the organic medium must be such that they lend good application properties to the dispersion.
• the organic medium is preferably formulated also to give appropriate wettability of the solids and the substrate, good drying rate, dried film strength sufficient to withstand rough handling, and good firing properties. Satisfactory appearance of the fired composition is also important.
• organic medium for most thick film compositions is typically a solution of resin in a solvent frequently also containing thixotropic agents and wetting agents.
• the solvent usually boils within the range of 130-350°C.
• resins such as ethylhydroxyethyl cellulose, wood rosin, mixtures of ethyl cellulose and phenolic resins, polymethacrylates of lower alcohols, and monobutyl ether of ethylene glycol monoacetate can also be used.
• Suitable solvents include kerosene, mineral spirits, dibutylphthalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, and high-boiling alcohols and alcohol esters. Various combinations of these and other solvents are formulated to obtain the desired viscosity and volatility.
• thixotropic agents which are commonly used are hydrogenated castor oil and derivatives thereof and ethyl cellulose. It is, of course, not always necessary to incorporate a thixotropic agent since the solvent/resin properties coupled with the shear thinning inherent in any suspension may alone be suitable in this regard.
• Suitable wetting agents include phosphate esters and soya lecithin.
• the ratio of organic medium to solids in the paste dispersions can vary considerably and depends upon the manner in which the dispersion is to be applied and the kind of organic medium used. Normally, to achieve good coverage, the dispersions will contain complementally by weight 40-90% solids and 60-10% organic medium.
• the pastes are conveniently prepared on a three-roll mill.
• the viscosity of the pastes is typically 20-150 Pa - s when measured at room temperature on Brookfield viscometers at low, moderate and high shear rates.
• the amount and type of organic medium (vehicle) utilized is determined mainly by the final desired formulation viscosity and print thickness.
• the resistor material of the invention can be made by thoroughly mixing together the glass frit, conductive phases and semiconductive phases in the appropriate proportions.
• the mixing is preferably carried out by either ball milling or ball milling followed by Y-milling the ingredients in water (or an organic liquid medium) and drying the slurry at 120°C overnight.
• the mixing is followed by calcination of the material at a higher temperature, preferably at up to 500°C, depending on the composition of the mixture. The calcined materials are then milled to 0.5-2 ⁇ or less average particle size.
• Such a heat treatment can be carried out either with a mixture of conductive and semiconductive phases and then mixed with appropriate amount of glass or semiconductive and insulative phases and then mixed with conductive phases or with a mixture of all functional phases.
• Heat treatment of the phases generally improves the control of TCR.
• the selection of calcination temperature depends on the melting temperature of the particular glass frit used.
• the termination material is applied first to the surface of a substrate.
• the substrate is generally a body of sintered ceramic material such as glass, porcelain, steatite, barium titanate, alumina or the like.
• a substrate of Alsimag @ alumina is preferred.
• the termination material is then dried to remove the organic vehicle and fired in a conventional furnace or a conveyor belt furnace in an inert atmosphere, preferably N 2 atmosphere.
• the maximum firing temperature depends on the softening point of the glass frit used in the termination composition. Usually this temperature varies between 750°C to 1200°C.
• the material cooled to room temperature there is formed a composite of glass having particles of conductive metals, such as Cu, Ni, embedded in and dispersed throughout the glass layer.
• the resistance material is applied in a uniform-drying thickness of 20-25 ⁇ m on the surface of the ceramic body which has been fired with the termination as described earlier.
• Compositions can be printed either by using an automatic printer or a hand printer in the conventional manner.
• the automatic screen printed techniques are employed using a 200-325 mesh screen.
• the printed pattern is then dried at below 200°C, e.g. to about 150°C for about 5-15 minutes before firing.
• Firing to effect sintering of the materials and to form a composite film is preferably done in a belt furnace with a temperature profile that will allow burnout of the organic matter of about 300 ⁇ 600°C, a period of maximum temperature of about 800-1000°C lasting about 5-30 minutes, followed by a controlled cooldown cycle to prevent unwanted chemical reactions at intermediate temperatures or substrate fracture of stress development within the film which can occur from too rapid cooldown.
• the overall firing procedure will preferably extend over a period of about 1 hour with 20-25 minutes to reach the firing temperature, about 10 minutes at the firing temperature, and about 20-25 minutes in cooldown.
• the furnace atmosphere is kept low in oxygen partial pressure by providing a continuous flow of N 2 gas through the furnace muffle.
• a positive pressure of gas must be maintained throughout to avoid atmospheric air flow into the furnace and thus an increase of oxygen partial pressure.
• the furnace is kept at 800°C and N 2 or similar inert gas flow is always maintained.
• the above-described pretermination of the resistor system can be replaced by post termination, if necessary. In the case of post termination, the resistors are printed and fired before terminating.
• HTCR hot temperature coefficient of resistance
• TCR Temperature Coefficient of Resistance
• a pattern of the resistor formulation to be tested is screen printed upon each of ten coded Alsimag 614 1 x 1" ceramic substrates and allowed to equilibrate at room temperature and then dried at 150°C.
• the mean thickness of each set of dried films before firing must be 22-28 microns as measured by a Brush Surfanalyzer.
• the dried and printed substrate is then fired for about 60 minutes using a cycle of heating at 35°C per minute to 850°C, dwell at 850°C for 9 to 10 minutes and cooled at a rate of 30°C per minute to ambient temperature. Resistance measurement and calculations
• test substrates are mounted on terminal posts within a controlled temperature chamber and electrically connected to a digital ohm-meter.
• the temperature in the chamber is adjusted to 25°C and allowed to equilibrate, after which the resistance of each substrate is measured and recorded.
• the temperature of the chamber is then raised to 125°C and allowed to equilibrate, after which the resistance of the substrate is again measured and recorded.
• TCR hot temperature coefficient of resistance
• R 25°c and Hot TCR are averaged and R 25°c values are normalized to 25 microns dry printed thickness and resistivity is reported at ohms per square at 25 microns dry print thickness. Normalization of the multiple test values is calculated with the following relationship: Coefficient of variance
• CV coefficient of variance
• Two thick film resistor compositions were formulated in the manner described above and resistors were formed therefrom.
• the two compositions contained both Ru0 2 and Ni metal as conductive materials and differed in the amount of Ni powder. Quite predictably, the additional amount of Ni metal resulted in lowering the resistivity of the resistors made therefrom.
• the composition of the materials and electrical properties of the resistors are given in Table 2 below.
• a processed powder was formed by ball milling the below-listed components in water for 22 hours and then allowing the dispersion to dry overnight. After drying, the powder was ball milled for 15 minutes in a plastic container using polyethylene balls as the grinding medium.
• the processed powder had the following composition:
• a further series of thick film resistor compositions was made in accordance with the invention in which each of three different resistor formulations was made using three different organic media.
• the data on the resistor made therefrom show that changes in the composition of the organic medium can be used to obtain different electrical properties for a resistor of given solids composition.
• the compositions of the functional phases are given in Table 5, the compositions of the three organic media are given in Table 6 and the electrical properties of the resistors made therefrom are given in Table 7 below.
• the mechanism by which the organic media changes the properties of the resistors with which they are used is not known with certainty. However, it is believed to be associated with the burning characteristics of each medium. For example, the formation of highly active carbon during firing may result in the formation of small amounts of carbides and/or oxycarbides which change the properties of the resistors. Such variation in the resistor properties would, however, be quite different if the resistor were fired in higher oxygen-containing atmospheres because such carbides and/or oxycarbides would be oxidized and thus removed from the system.

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• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Manufacturing & Machinery (AREA)
• Physics & Mathematics (AREA)
• Electromagnetism (AREA)
• Non-Adjustable Resistors (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Glass Compositions (AREA)
• Apparatuses And Processes For Manufacturing Resistors (AREA)

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• 1984
  • 1984-12-17 US US06/682,299 patent/US4645621A/en not_active Expired - Fee Related
• 1985
  • 1985-12-12 CA CA000497473A patent/CA1248749A/en not_active Expired
  • 1985-12-13 IE IE3151/85A patent/IE56953B1/xx unknown
  • 1985-12-13 EP EP85115900A patent/EP0185322B1/en not_active Expired
  • 1985-12-13 DE DE8585115900T patent/DE3571288D1/de not_active Expired
  • 1985-12-16 DK DK582285A patent/DK582285A/da not_active Application Discontinuation
  • 1985-12-16 KR KR1019850009442A patent/KR900004078B1/ko not_active IP Right Cessation
  • 1985-12-17 GR GR853028A patent/GR853028B/el unknown
  • 1985-12-17 JP JP60282141A patent/JPH0622161B2/ja not_active Expired - Lifetime

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